CN108025293A - Conjugated diene catalyst for producing and its manufacture method - Google Patents

Abstract

The present invention provides a kind of load formed catalyst and its manufacture method, the load formed catalyst by catalytic oxidative dehydrogenation in the reaction of conjugated diene is manufactured by the mixed gas of the monoolefine comprising carbon number more than 4 and molecular oxygen, it is possible to increase hardness and the long-time stability for improving reaction.A kind of conjugated diene manufacture formed catalyst, it is the catalyst for reacting manufacture conjugated diene by catalytic oxidative dehydrogenation for the mixed gas by the monoolefine comprising carbon number more than 4 and molecular oxygen, wherein, the catalyst is obtained by the way that metal composite oxide is shaped with glass fibres inorganic assistant.

Description

Conjugated diene catalyst for producing and its manufacture method

Technical field

Pass through catalysis oxidation the present invention relates to the mixed gas by the monoolefine comprising carbon number more than 4 and molecular oxygen Dehydrogenation reaction manufactures the catalyst and its manufacture method of conjugated diene.

Background technology

In the past, the butadiene as the raw material of synthetic rubber etc. industrially by the thermal decomposition of naphtha cut and carried Take and manufacture, but worry the deterioration of the stable supplying to market from now on, therefore it is required that the manufacture method of new butadiene.Cause This, pays close attention to and carries out oxidative dehydrogenation to n-butene in the presence of a catalyst by the mixed gas comprising n-butene and molecular oxygen Method.However, as caused by target product and/or byproduct of reaction coke shape material separate out or be attached to catalyst surface, In inert substance, reaction tube, in subsequent handling equipment, thus, the resistance for causing the circulation of reacting gas in industrial plant is worried Hinder, the blocking of reaction tube, with the various problems such as the shut-down of this associated factory, the reduction of yield.In order to avoid the above problem, In industrial plant, usually reaction is stopped before blocking is produced, and pass through the block part of reaction tube, subsequent handling equipment etc. Heating etc. be flared off the regeneration treatment of coke shape material, but the stopping of reaction of steady running is carried out at regeneration Reason, can cause the economy of industrial plant to be deteriorated, it is therefore desirable for suppressing the generation of coke shape material as much as possible.

In addition, as another problem in the manufacture method of butadiene, the breakage of catalyst can be enumerated.Catalyst Breakage be conjugated diene manufacturing process in distinctive phenomenon, its for catalyst by long reaction and from filling when shape Change or deterioration and (breakage) out of shape into catalyst plate, i.e. fragment shape, graininess, be further powdery, so as to worry following The problem of cited.That is, worry：Because after breakage catalyst plate accumulate caused by reactor the increase of the pressure loss, From partly accumulating the catalyst plate after undesirable side reaction and breakage caused by the catalyst in reactor to follow-up Being mixed into the purification system in stage, on countermeasure of the prior art, document as follows is known.

Patent document 1 discloses the change in outside diameter and the correlation of Strength Changes of the front and rear catalyst of reaction.As special The tabletting of the manufacturing process of the catalyst of sharp document 1 is formed in following aspect, and there are problem：The mechanical strength of catalyst becomes higher, separately On the one hand, due to so that the mode of catalytic active component densely aggegation is formed, coke shape material easily by Side reaction and generate and/or be detained in catalytic inner, and compared with the catalyst as obtained from other manufacturing process, Easily separate out coke shape material；Reaction heat is also easily accumulated in catalytic inner, so that yield reduction or runaway reaction occur；This Outside, the producing rate variance of catalyst in itself.Patent document 2 discloses that percentage of damage and coke shape material growing amount in catalyst filling Correlation, but do not disclose with the catalyst or reaction condition for suppressing percentage of damage in long reaction it is relevant in Hold.

As the damaged means for solving catalyst, the means for improving the hardness of catalyst in itself can be enumerated. In the past, the evaluation method as mechanical strength used in those skilled in the art, can enumerate wear intensity described later, it is table Show the physics value of the damaged degree of impact when being filled relative to catalyst, as the evaluation method of mechanical strength, Ke Yilie Lift problem as shown below.That is, in wear intensity evaluation, since the mechanical load for putting on catalyst is low, as described later Even the good catalyst of wear intensity, also observes breakage because of long reaction.On the other hand, tensile and compression testing machine is being used In hardness evaluation, the correlation between the catalyst breakage as caused by long reaction can be significantly confirmed as described later, Therefore compared with the conventional wear intensity evaluation as mechanical strength evaluation, stringent and suitable evaluation of physical property can be carried out.Separately Outside, as described later, in the good catalyst of wear intensity, low and damaged because of the long reaction feelings of hardness are also observed Condition, represents that with the evaluation of physical property method of the dependency relation of the catalyst breakage as caused by long reaction be not known.

As with formed catalyst it is relevant it is common be used for for improving the method for mechanical strength, following document is public Know.

Patent document 3 to patent document 9 all refers to addition with specific particle diameter distribution, fibre length, acid strength etc. Organic additive or/and the catalyst of inorganic assistant or its manufacture method, the evaluation method of mechanical strength corresponds to be led by filling The pulverization rate of cause or the evaluation of foregoing wear intensity, it is unknown to the effect of raising hardness.That is, shaping is particularly loaded in formed catalyst In catalyst, with improve mechanical strength particularly the species of the auxiliary agent of hardness or additive amount it is relevant find patent document 3 to Do not recorded in patent document 9, therefore to those skilled in the art nor known.

When catalyst is considered as ceramic material, in addition to the addition of inorganic assistant, as the method for improving hardness, may be used also To enumerate the control of the pore structure as shown in non-patent literature 1.Breakage on catalyst, it is believed that be by long reaction Or caused by the stress of the catalytic inner in regeneration treatment, it can be speculated as causing brokenly in the ambient stress rise of pore Damage.That is, in order to suppress the preferred reduction pore of the breakage of catalyst, but in non-patent literature 1, shaped not in load Organic additive is not added in catalyst completely and improves the record of hardness, this is not known.

In addition, from the viewpoint of the economy in industrial plant, can be to obtain the fourth as target product in high yield Diene this point is certainly also important.Butadiene yield is low then to represent that the yield of accessory substance is relatively high, in the case in order to obtain The butadiene of high-purity as the final products in industrial plant, it is necessary to the purification system of higher performance, worry these equipment into Originally become higher.Worry undesirable side reaction occurs because adding the auxiliary agent for being used for improving hardness.I.e., it is desirable to develop a kind of catalysis Agent, it does not reduce butadiene growing amount, does not increase accessory substance growing amount, and suppresses the broken of the catalyst as caused by long reaction Damage.

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2011-241208 publications

Patent document 2：Japanese Unexamined Patent Publication 2012-046509 publications

Patent document 3：No. 3313863 publications of Japanese Patent Publication No.

Patent document 4：No. 4863436 publications of Japanese Patent Publication No.

Patent document 5：Japanese Unexamined Patent Publication 2002-273229 publications

Patent document 6：No. 5388897 publications of Japanese Patent Publication No.

Patent document 7：No. 2012/036038 separate edition of International Publication No.

Patent document 8：No. 5628936 publications of Japanese Patent Publication No.

Patent document 9：Japanese Unexamined Patent Publication 07-16463 publications

Non-patent literature

Non-patent literature 1：Palace Tian Sheng, god are wild rich, " material " 32,354, P102-108

The content of the invention

Problems to be solved by the invention

It is an object of the invention to provide a kind of catalyst and its manufacture method, the catalyst takes off by catalysis oxidation , can in reaction of the hydrogen by the mixed gas of the monoolefine comprising carbon number more than 4 and molecular oxygen manufacture conjugated diene Improve the long-time stability of reaction, and the hardness of the catalyst improves.

Means for solving the problems

The present inventor has made intensive studies to solve aforementioned problems, it turns out that, by adding glass fibres Inorganic assistant, can improve hardness in the case where not reducing the yield as the conjugated diene of target product, can be notable Suppress the breakage of the catalyst as caused by long reaction, so as to solve aforementioned problems, be finally completed the present invention.

The present invention has the feature of following (1) to (7) alone or in combination.That is, the present invention relates to following invention：

(1) a kind of conjugated diene manufacture formed catalyst, its be for by catalytic oxidative dehydrogenation reaction by comprising The catalyst of the monoolefine of carbon number more than 4 and the mixed gas manufacture conjugated diene of molecular oxygen, it is characterised in that institute Conjugated diene manufacture formed catalyst is stated by shaping metal composite oxide and glass fibres inorganic assistant to obtain Arrive；

(2) the conjugated diene manufacture formed catalyst as described in (1), it is characterised in that the conjugated diene system Make the condition for meeting following formula (A) with formed catalyst：

R (=La/Dc)≤45 (A)

(in formula, La is the average fiber length of glass fibres inorganic assistant, and Dc is the average grain of metal composite oxide Footpath)；

(3) the conjugated diene manufacture formed catalyst as described in (1) or (2), wherein, the conjugated diene manufacture Organic additive is free of with formed catalyst；

(4) the conjugated diene manufacture formed catalyst as any one of (1) to (3), wherein, composition metal oxygen Compound meets following composition formulas (D),

Mo_l2Bi_aFe_bCo_cNi_dX_eY_fZ_g (D)

(in formula, X is represented selected from lithium, sodium, potassium, rubidium, at least one of caesium alkali metal, Y represent selected from magnesium, calcium, At least one of strontium, barium alkali earth metal, Z are represented in lanthanum, cerium, praseodymium, neodymium, samarium, europium, antimony, tungsten, lead, zinc, cerium, thallium At least one element, a, b, c, d, e and f each represent bismuth, iron, cobalt, nickel, X, Y and Z relative to molybdenum 12 atomic ratio, In 0.3 ＜ a ＜ 3.5,0.6 ＜ b ＜ 3.4,5 ＜ c ＜ 8,0 ＜ d ＜ 3,0 ＜ e ＜ 0.5,0≤f≤4.0,0≤g≤2.0 model Enclose, g is the numerical value for the state of oxidation for meeting other elements.)；

(5) the conjugated diene manufacture load formed catalyst as any one of (1) to (4), it is for leading to Cross catalytic oxidative dehydrogenation reaction and conjugated diene is manufactured by the mixed gas of the monoolefine comprising carbon number more than 4 and molecular oxygen The catalyst of hydrocarbon, it is characterised in that metal composite oxide is carried on carrier with glass fibres inorganic assistant and is obtained；

(6) a kind of manufacture method of conjugated diene manufacture formed catalyst, it is any one of (1) to (5) Conjugated diene manufacture formed catalyst manufacture method, wherein, the manufacture method includes following process：

The chemical combination for including each metal containing metal composite oxide is prepared more than 20 DEG C and under conditions of less than 90 DEG C The mixed solution or slurry of thing, are then dried the mixture, precalcining are carried out, with glass fibres inorganic assistant one Shaping is played, is formally calcined；

(7) manufacture method of the conjugated diene manufacture formed catalyst as described in (6), wherein, the temperature of precalcining For more than 200 DEG C and less than 600 DEG C, and formal calcining heat is more than 200 DEG C and less than 600 DEG C；

(8) the conjugated diene manufacture manufacture method of load formed catalyst as described in (6) or (7), it has Metal composite oxide and glass fibres inorganic assistant are coated on to the forming process of carrier together with binding agent, and is catalyzed and lives Property component load factor be more than 20 weight % and below 80 weight %, and the average grain diameter of catalyst for more than 3.0mm and Below 10.0mm；

(9) manufacture method of the formed catalyst as any one of (6) to (8), wherein, in whole manufacturing process In, without using organic additive.

Invention effect

According to the present invention it is possible to obtain it is a kind of can by catalytic oxidative dehydrogenation by the list that includes carbon number more than 4 Used in the reaction of the mixed gas of alkene and molecular oxygen manufacture conjugated diene, catalyst that hardness is high, and due to can To suppress the breakage of the catalyst in long reaction, therefore a kind of catalyst with long-time stability and its manufacture can be provided Method.

Embodiment

A kind of conjugated diene catalyst for producing and its manufacture method, the catalyst can be used for passing through catalysis oxidation Dehydrogenation reaction is manufactured the reaction of conjugated diene by the mixed gas of the monoolefine comprising carbon number more than 4 and molecular oxygen, It can be preferably used for manufacturing butadiene by the mixed gas comprising n-butene and molecular oxygen by catalytic oxidative dehydrogenation reaction In reaction.Hereinafter, to addition glass fibres inorganic assistant and the conjugated diene manufacture of the invention that is formed with urging Agent and its manufacture method illustrate.

In the present invention, n-butene refers to single among 1- butylene, trans-2-butene, cis-2-butene, isobutene The gas of component or the mixed gas for including at least one component, refer to 1,3-butadiene for butadiene is tightened up.

The glass fibres inorganic assistant used in the catalyst of the present invention is primarily referred to as, by 600 DEG C of heat The inorganic matter arbitrary naturally producing and/or artificial also not burnt in reason handled more than glass transition temperature from And the arbitrary fibrous or bar-shaped auxiliary agent prepared, and its will not all be burnt by formal calcination process described later. Since glass fibres inorganic assistant can also remain in formal calcination process described later, have composition metal oxygen The effect that compound (precalcining powder) is coupled each other, produces and also suppresses even if when generating the load for causing breakage in the catalyst Damaged effect.In the present invention, the material as glass fibres inorganic assistant, Mohs' hardness are not particularly limited, such as It is preferred that by arbitrary sulfide mineral, oxide mineral, halogenation mineral, inorganic acid salt mineral, humatite etc. alone or in combination and Material (this hair that the Mohs' hardness among the material obtained from is more than 2 is heat-treated more than glass transition temperature Bright glass), for the raw material of these materials, further preferred inorganic acid salt mineral, most preferably silicate mineral, such as Glass fibre or chopped strand can be enumerated.In addition, for glass fibres inorganic assistant, pass through respective either alone or in combination Acid treatment, alkali process and silane treatment etc. are implemented in ground, and it is preferable to become nonactive aspect in catalyst reaction.

In addition, the average fiber length of glass fibres inorganic assistant preferably satisfies the condition represented by following formula (A), more The condition represented by following formula (B) is preferably satisfied, most preferably meets the condition represented by following formula (C).Glass fibres are inorganic Auxiliary agent can easily be obtained from such as Central Glass Co., Ltd., Nitto Boseki Co. Ltd etc..In addition, glass fibers The average grain diameter for tieing up shape inorganic assistant is preferably 0.1 μm to 100 μm, more preferably 1 μm to 50 μm.Glass fibres inorganic assistant Average fiber length be preferably 10 μm to 4000 μm, more preferably 50 μm to 500 μm.

R (=La/Dc)≤45 (A)

0.5≤R (=La/Dc)≤20 (B)

1≤R (=La/Dc)≤10 (C)

(in formula, La is the average fiber length of glass fibres inorganic assistant, and Dc is the average grain of metal composite oxide Footpath.)

In the present invention, metal composite oxide, the average grain diameter of organic additive for example calculate by the following method.

As device, it is not particularly limited, such as the LMS-2000e manufactured using Western Hills manufacturing company, use purifying Scattered light intensity is set as about 4.0 to about 6.0 and is surveyed by water as decentralized medium and by various Sample introduction sample cells It is fixed, average grain diameter is calculated by the particle diameter distribution obtained with quality percentage.

The average grain diameter of metal composite oxide is preferably 1 μm to 500 μm, more preferably 10 μm to 100 μm.

In the catalyst of the present invention or its manufacture method, organic additive is not preferably added or used to.

Metal composite oxide in the present invention preferably satisfies following composition formulas (D).

Mo_l2Bi_aFe_bCo_cNi_dX_eY_fZ_g (D)

(in formula, X is represented selected from lithium, sodium, potassium, rubidium, at least one of caesium alkali metal, Y represent selected from magnesium, calcium, At least one of strontium, barium alkali earth metal, Z are represented in lanthanum, cerium, praseodymium, neodymium, samarium, europium, antimony, tungsten, lead, zinc, cerium, thallium At least one element, a, b, c, d, e and f each represent bismuth, iron, cobalt, nickel, X, Y and Z relative to molybdenum 12 atomic ratio, In 0.3 ＜ a ＜ 3.5,0.6 ＜ b ＜ 3.4,5 ＜ c ＜ 8,0 ＜ d ＜ 3,0 ＜ e ＜ 0.5,0≤f≤4.0,0≤g≤2.0 model Enclose, g is the numerical value for the state of oxidation for meeting other elements.)

Raw material for each metallic element for the catalyst for obtaining the present invention is not particularly limited, and can use comprising at least A kind of nitrate, nitrite, sulfate, ammonium salt, acylate, acetate, carbonate, the basic carbonate of each metallic element Salt, chloride, inorganic acid, the salt of inorganic acid, heteropoly acid, the salt of heteropoly acid, hydroxide, oxide, metal, alloy etc. or Their mixture of person.Wherein preferably nitrate raw material.

The preparation method of the catalyst of the present invention is not particularly limited, and is preferably as follows method：Made in the form of a powder For the metal composite oxide of the active ingredient of catalyst, then carried out in the case where not being added or used to organic additive into Shape, records detailed content below.It should be noted that describe the order of each operation below as preferable example, but with Do not limited in the combined aspects of the order for each operation for obtaining final catalyst prod, process number, each operation.

Process (A1) is allocated and drying

The mixed solution or slurry of the raw material of catalytic active component are prepared, by the precipitation method, gelling technique, co-precipitation The processes such as method, hydrothermal synthesis method, then using known in spray drying process, evaporation drying method, cylinder drying, freeze-drying etc. Drying means, obtain the present invention drying powder.Can be water, organic as solvent on the mixed solution or slurry Any one in solvent or their mixed solution, the material concentration of the active ingredient of catalyst does not also limit, this Outside, the allotment such as the liquid temperature for the mixed solution or slurry, atmosphere condition and drying condition are not particularly limited, but should Consider the performance of final catalyst, mechanical strength, formability, production efficiency etc. and select appropriate scope.Wherein, in this hair Following method is most preferably in bright：The mixing of the raw material of the active ingredient of catalyst is formed under conditions of 20 DEG C to 90 DEG C Solution or slurry, are conducted into spray dryer so that dryer export temperature be 70 DEG C to 150 DEG C, it is obtained dry The average grain diameter of dry powder be 10 μm to 700 μm of mode adjust hot-wind inlet temperature, the pressure inside spray dryer and The flow of slurry.In addition, from the mixed solution of this process or slurry be prepared into foregoing drying untill, added with arbitrary amount Glass fibres inorganic assistant or/and organic additive described later is added to fall within the manufacture method of the catalyst of the present invention.

Process (A2) precalcining

More than 200 DEG C and less than 600 DEG C carry out precalcining to the drying powder obtained in this way, can obtain Average grain diameter is 10 μm to 100 μm of metal composite oxide (precalcining powder) of the invention.In the present invention, sometimes will be multiple Close metal oxide and be known as precalcining powder.On the condition of the precalcining, atmosphere during for calcination time, calcining does not have yet Especially limitation, the method for calcining are also not particularly limited to fluid bed, rotary kiln, Muffle furnace, tunnel type calcining furnace etc., it is contemplated that The performance of final catalyst, mechanical strength, formability, production efficiency etc. and select appropriate scope.Wherein, in the present invention Carried out in air atmosphere 1 hour to 12 more than 300 DEG C and in less than 600 DEG C of scope most preferably in tunnel type calcining furnace The method of hour.In addition, before the precalcining of this process or after precalcining, glass fibres described later are added with arbitrary amount Inorganic assistant and organic additive fall within the manufacture method of the catalyst of the present invention.

Process (A3) shapes

In the present invention, the precalcining powder obtained in this way is shaped and used.The shape of formed products is not special Spherical, cylindric, ring-type etc. are not limited to, but should be considered by a series of preparation and the machine in the catalyst that finally obtains Tool intensity, reactor, the production efficiency etc. for preparing and make choice.For manufacturing process it is not also specifically limited, will be following Shown carrier or organic additive, glass fibres inorganic assistant, binding agent etc. make an addition to precalcining powder and are configured to cylinder When shape, ring-type, using tabletting forming machine, extrusion shaper etc., using comminutor etc. when spherically shaped, so as to be shaped Product.Wherein, in the present invention, it is preferred to which above-mentioned glass fibres inorganic assistant is added together with precalcining powder and is formed Method；Further preferably above-mentioned glass fibres inorganic assistant is added together with precalcining powder and by rotating comminution granulation Coated on inert carrier and carry out the method for loading shaping；When being coated by rotating comminution granulation, do not add completely most preferably Add organic additive.

For the material of carrier, aluminium oxide, silica, titanium dioxide, zirconium oxide, niobium oxide, two can be used Material known to silica-alumina, carborundum, carbide and their mixture etc., in addition, for its particle diameter, water suction Rate, mechanical strength, the crystallinity of each crystalline phase, mixed proportion etc. are it is not also specifically limited, should consider the property of final catalyst Energy, formability, production efficiency etc. and select appropriate scope.On the ratio of the mixing of carrier and precalcining powder, according to each The input weight of raw material, load factor is calculated by following formula.

Load factor (weight %)=(weight of the precalcining powder used in formation)/{ (what is used in formation is pre-calcined Burn the weight of powder)+(weight of the carrier used in formation) } × 100

Relative to the weight of precalcining powder, the additive amount of glass fibres inorganic assistant is preferably 0.1 weight % to 25 Weight %, particularly preferably 0.3 weight % to 10 weight %, are most preferably 0.5 weight % to 5 weight %.In addition, to glass Material and component composition it is not also specifically limited, more preferably such as E glass alkali-free glass, to have carried out silane treatment etc. various The glass of deactivation processing chemically, because they are without generating accessory substance for catalyst reaction etc. no Good influence.In addition, on glass fibres inorganic assistant, pulverizing process can be implemented before formation, the method for crushing does not have Especially limitation, such as by ball mill, rod mill, SAG grinding machines, airslide disintegrating mill, autogenous tumbling mill, hammer-mill, granulator, disc mill Machine, roller mill, high pressure pulverizing rolling, VSI grinding machines etc. are implemented alone or in combination, and the object of the crushing can be individually for glass fibers Tie up shape inorganic assistant or be mixed with the mixture for the catalyst raw material that precalcining powder etc. adds in forming process.

In the present invention, organic additive is mainly had by the heat treatment by more than 200 DEG C and less than 600 DEG C and what is burnt Arbitrary powdery that machine thing is formed, graininess, threadiness, squamaceous auxiliary agent, and by formal calcination process described later, its It is some or all to burn, such as can enumerate：The polymer or polymeric beads, high water absorption of polyethylene glycol, various esters etc. The hirudo leech of property resin either have hydroscopic substance, various surfactants, wheat flour or purifying starch of arbitrary water absorption rate etc. The cellulose and its derivates of various starch and crystallinity or amorphous.It is believed that organic additive pass through it is formal Calcination process and burn and as described later in the catalyst formed gap when, in the catalyst produce cause breakage load when its The stress of surrounding becomes higher, and as a result becomes that breakage easily occurs, therefore in manufacture catalyst of the invention, does not preferably add organic Auxiliary agent.Relative to the average grain diameter of precalcining powder, the model of the average grain diameter of the organic additive in the present invention 0.001 to 1000 In enclosing.

Here, the binding agent in the present invention refers to, by the average grain diameter selected from its molecular diameter relative to precalcining powder The compound of compound group in scope below 0.001 passes through alone or in combination and the liquid formed, such as can arrange Lift material as described below.That is, the organic solvent of liquid, the dispersion of organic matter, water-miscible organic solvent and they and water Arbitrary proportion mixture, be not particularly limited, the aqueous solution or ion exchange water of the polyalcohol such as preferably glycerine, further The most preferably ion exchange water from the viewpoint of formability.Since binding agent includes water or organic matter, one part or Person all burns in formal calcination process described later.In general, when compared with the average grain diameter of precalcining powder, binding agent The molecular diameter of the middle organic matter used is sufficiently small, therefore even if using binding agent, is also unable to reach as organic additive The discovery of the formation in gap in the catalyst, according to the present invention people, does not confirm aobvious even if the species for changing binding agent yet The firmness change of work.In addition, by the binding agent use aforementioned catalytic agent raw material solution, can also with process (A1) Element is incorporated into the outmost surface of catalyst by different modes.

In the method for the load shaping based on coating, relative to 100 parts by weight of precalcining powder, the usage amount of binding agent Preferably 2 parts by weight are more preferably 10 parts by weight to 50 parts by weight to 60 parts by weight.The reaction of the present invention is anti-for oxidative dehydrogenation Should, and be exothermic reaction, therefore, because the heat dissipation of catalytic inner, further as passing through generated conjugated diene Diffusion is effectively performed and suppresses the generation and/or delay of coke shape material, therefore it is most preferred manufacturing process to load shaping.

Process (A4) is formally calcined

The precalcining powder or formed products obtained in this way preferably before for reaction more than 200 DEG C and 600 DEG C are calcined (formal calcining) again below.On formal calcining, atmosphere during for calcination time, calcining is without spy Do not limit, the method for calcining is also not specially limited in fluid bed, rotary kiln, Muffle furnace, tunnel type calcining furnace etc., it is contemplated that The performance of final catalyst, mechanical strength, production efficiency etc. and select appropriate scope.Wherein, in the present invention most preferably , carried out in air atmosphere more than 300 DEG C and within the scope of less than 600 DEG C of temperature in tunnel type calcining furnace 1 it is small when To 12 calcinings when small.

Whole manufacturing process in the present invention is from catalyst raw material untill obtaining the catalyst of the present invention, passes through By process (A1) to process (A4) alone or in combination obtained from whole process.In the present invention, forming process is process (A3) it is some or all among.

On the catalyst being prepared more than, its shape, size are not particularly limited, but consider filling extremely During pressure loss in reaction tube after the workability of reaction tube and filling etc., preferably spherical shape, average grain diameter is preferred For 3.0mm to 10.0mm, in addition the load factor of catalytic active component is preferably 20 weight % to 80 weight %.

In the present invention, the wear intensity as the index for representing mechanical strength calculates by the following method.As device, make The Tab attrition degree exerciser manufactured with woods Physicochemical company, by speed setting for 25rpm, will be set as 10 minutes processing time And 50g catalyst samples are handled, then the part of abrasion is sieved using the standard screen that screen size is 1.70mm, is surveyed Surely the catalyst weight on sieve is remained in, is calculated by following formula.The value of wear intensity is smaller, then mechanical strength is more excellent, It is, for example, below 3 weight % for preferable scope, more preferably below 1.5 weight %, more preferably 0.5 weight Measure below %.

Wear intensity (weight %)=100 × [(catalyst weight-remain in the catalyst weight on sieve)/catalyst weight]

In the present invention, the hardness as the index for representing mechanical strength calculates by the following method.As device, do not have Especially limitation, such as using tensile and compression testing machine (the Techno Graph TG5kN that Minebea companies manufacture), connect special accessories And catalyst 1 is placed, load speed is set as 2mm/ minutes in a compressed mode, obtains displacement-load curves.Continuously Mechanical load is applied to catalyst, more than the 5% of load reduction peak or the reduction of more than 0.1kgf or is being catalyzed When crackle (rupture) is visually confirmed in agent, stop evaluation immediately, using the maximum of displacement-load curves as catalyst Hardness.The evaluation is implemented with the catalyst of more than 30, is averaged value as hardness.Below in an example, on hard Degree, records the hardness obtained using tensile and compression testing machine, but the hardness of the present invention on more broadly from the limitation of its mode, gas room If formula hardness, Vickers hardness etc. are being observed that and the damaged significantly correlated hardness of the catalyst as caused by long reaction In the range of evaluation, then comparably it is considered as hardness.It is hard except foregoing multiple catalyst as the index of mechanical strength Beyond the average value of degree, the benchmark of the deviation of the hardness of multiple catalyst can also be applied, such as it is assumed that hardness is divided in normal state Standard deviation in the case of cloth etc., it is assumed that hardness in Weiber coefficient etc. in the case of Wei Buer distributions and multiple Minimum of the hardness of catalyst etc..

The bar of the reaction of conjugated diene is manufactured by the monoolefine of carbon number more than 4 on the catalyst using the present invention Part, forms as unstrpped gas, uses the monoolefine comprising 1 volume % to 20 volume %, the molecule of 5 volume % to 20 volume % Non-active gas, such as nitrogen, the dioxy of state oxygen, the vapor of 0 volume % to 60 volume % and 0 volume % to 94 volume % Change the mixed gas of carbon, the scope that reaction bath temperature is 200 DEG C to 500 DEG C, reaction pressure is pressure of the normal pressure to 10 atmospheric pressure Under power, unstrpped gas is relative to the air speed (GHSV) of the catalyst mouldings of the present invention when 350 is small^-1To 7000 it is small when^-1Model In enclosing.As the form of reaction, do not limited among fixed bed, moving bed and fluid bed, preferably fixed bed.

In the present invention, the breakage of catalyst is by making in the presence of a catalyst by the monoene of carbon number more than 4 Hydrocarbon manufactures the reaction long reaction of conjugated diene, and catalyst mechanical strength in itself reduces, and catalyst is from shape during filling Change or deterioration and (breakage) out of shape fragmentates shape, be further the phenomenon of powdery；For reason, it may be considered that be： Breakage caused by the generation of coke shape material from catalytic inner, and/or by the combustion heat based on regeneration treatment or Breakage etc. caused by the expansion of the violent burning gases of person.Worry triggers following problem due to the breakage of catalyst：Because of breakage Rear catalyst plate accumulates caused by reactor the increase of the pressure loss, by partly accumulating in the catalysis in reactor Undesirable reaction and being mixed into the purification system of follow-up phase caused by agent.

In the present invention, mechanical strength is to be filled present in foregoing wear intensity and hardness, other patent documents 3 etc. Pulverization rate etc., as obtained from intensity evaluation measurement result general name, the intensity evaluation is by one or more Catalyst applies intensity evaluation obtained from some physics or mechanical load.

In the present invention, coke shape material is in the reaction of manufacture conjugated diene, utilizes reaction raw materials or target In product or byproduct of reaction at least any one generation material, its chemical composition, formation mechanism details still not Clearly, but due to separating out or being attached to catalyst surface, inert substance, in reaction tube or in subsequent handling equipment, particularly It is to cause the stopping for hindering the circulation of reacting gas, causing blocking or the reaction associated with it of reaction tube in industrial plant The reason for etc. various problems material.Further, it is usually stifled in generation in industrial plant for the purpose for avoiding foregoing problems Reaction is stopped before plug, and heating of block part by reaction tube or subsequent handling equipment etc. etc. carries out being flared off Jiao The regeneration treatment of charcoal shape material.In addition, for formation mechanism as the coke shape material, such as be presumed as follows.I.e., it is possible to Enumerate：The molybdenum compound separated out during because using O composite metallic oxide catalyst containing molybdenum using distilling in reactor is plays Point the polymerization of various olefines and the condensation of higher-boiling compound and generate the mechanism of coke shape material；Because with catalyst and instead Answer the abnormal Acid and basic sites in device, the polymerization of various olefines and the condensation of higher-boiling compound that free radical generation point is starting point And generate the mechanism of coke shape material；Diels-Alder reactions that reason conjugated diene and other olefin(e) compounds carry out and The generation of caused higher-boiling compound and condensation in reactor at the relatively low point of local temperature and generate coke shape material Mechanism etc., it is known that various mechanism in addition to the foregoing.

The catalyst of the present invention preferably at least has certain wear intensity before starting the reaction as shown below, further excellent Choosing has certain hardness.In the past, the evaluation method as mechanical strength used in those skilled in the art, after can enumerating The wear intensity stated, the physics value of the damaged degree of impact when it is represents to fill relative to catalyst, as mechanical strength Evaluation method, can enumerate problem as shown below.That is, in wear intensity evaluation, due to putting on the mechanical load of catalyst It is low, even therefore the good catalyst of wear intensity also observes breakage because of long reaction sometimes as described later.On the other hand, Compared to the conventional wear intensity evaluation as mechanical strength evaluation, tensile and compression testing machine is stringent and suitable evaluation of physical property side Method, this is because in hardness evaluation, to the problem of the present invention, tensile and compression testing machine can compatibly apply high mechanical load, such as The correlation that can be significantly confirmed between the breakage of the catalyst as caused by long reaction afterwards.But herein below As previously described to those skilled in the art nor known：As described later, even in the good catalyst of wear intensity In, also observe low and damaged because of the long reaction situation of hardness, as described herein hardness evaluation as represent with by The evaluation of physical property method of the damaged dependency relation of catalyst caused by long reaction is suitable.

Wear intensity be subject to shaping when add various intensity enhancers, the species of binding agent, amount or combinations thereof, The atomic ratio of catalyst composition, the phase morphology of each crystalline phase and their ratio, the further shape in allotment process, drying process Into the various preparation sections such as diameter, geometric structure and the aggegation form of second particle of catalytic active component shadow Ring, and also there is close relationship with the performance of catalyst, this is known, its numerical value is preferably below 2 weight %.It is another Aspect, on the knowledge opinion for improving hardness, particularly as the present invention in formed catalyst specifically The known document shown, as it was previously stated, confirm can be inorganic by adjusting organic additive or/and glass fibres by the present inventor The species of auxiliary agent and additive amount so as to fulfill hardness raising.

Embodiment

Hereinafter, the present invention is described in more detail by embodiment, the present invention without departing from its purport, then be not limited to Under embodiment.It should be noted that following, % refers to a mole % in the case of no particularly explanation.In addition, it is following, Shown in n-butene conversion, butadiene yield, TOS are defined as follows.

N-butene conversion (mole %)=(molal quantity of the n-butene reacted/molal quantity of the n-butene supplied) ×100

Butadiene yield (mole %)=(molal quantity of the butadiene generated/molal quantity of the n-butene supplied) × 100

TOS=mixed gas currency (hour)

Embodiment 1

(preparation of catalyst 1)

800 parts by weight ammonium heptamolybdates are dissolved completely in 3000 parts by weight to be heated in 80 DEG C of pure water (mother liquor 1).Connect , 11 parts by weight cesium nitrates are dissolved in 124ml pure water, and add to mother liquor 1.Then, by 275 parts by weight ferric nitrates, 769 Parts by weight cobalt nitrate and 110 parts by weight nickel nitrates are dissolved in 612ml and are heated in 60 DEG C of pure water, and add to mother liquor 1.Connect , 165 parts by weight bismuth nitrates are dissolved in and are heated to 60 DEG C by the way that 42 parts by weight nitric acid (60 weight %) are added to 175ml In aqueous solution of nitric acid obtained from pure water, and add to mother liquor 1.The mother liquor 1 is dried by spray drying process, and to gained To drying powder 440 DEG C, 5 it is small when under conditions of carried out precalcining.To the precalcining powder obtained in this way (average grain diameter：63.2 μm, according to the atomic ratio that calculates of input raw material be Mo:Bi:Fe:Co:Ni:Cs=12:1.7:1.8: 7.0:1.0:0.15) the crystallinity cellulose (average grain diameter of 5 weight % components is added：89.3 μm) and 3 weight % components Glass fibre (avarage fiber diameter after silane treatment：11 μm, average fiber length：150 μm), and be sufficiently mixed, so Afterwards by rotating comminution granulation, using relative to the 33 weight % glycerites that precalcining powder is 33 weight % as binding agent, So that the mode that load factor is 50 weight % loads and is configured to ball on inert spheroid carrier (silica-alumina) Shape.By the spherical formed products obtained in this way 500 DEG C, 5 it is small when under conditions of calcine so that obtained the present invention Catalyst 1.The wear intensity of catalyst 1 is 0.20 weight %, and hardness is 4.5kgf (44.0N).

Embodiment 2

(preparation of catalyst 2)

It with the addition of the crystallinity cellulose (average grain diameter of 5 weight % components to the precalcining powder obtained in embodiment 1： 89.3 μm) and the silane treatment of 3 weight % components after glass fibre (avarage fiber diameter：11 μm, average fiber length： 100 μm), in addition, catalyst is being prepared under the same conditions with catalyst 1, so as to obtain the catalyst 2 of the present invention. The wear intensity of catalyst 2 is 0.19 weight %, and hardness is 3.2kgf (31.4N).

Embodiment 3

(preparation of catalyst 3)

It is (flat to the addition of the glass fibre after the silane treatment of 3 weight % components to the precalcining powder obtained in embodiment 1 Equal fibre diameter：11 μm, average fiber length：150 μm), in addition, catalysis is being prepared under the same conditions with catalyst 1 Agent, so as to obtain the catalyst 3 of the present invention.The wear intensity of catalyst 3 is 0.42 weight %, hardness 15.5kgf (151.9N)。

Embodiment 4

(preparation of catalyst 4)

It with the addition of the crystallinity cellulose (average grain diameter of 5 weight % components to the precalcining powder obtained in embodiment 1： 89.3 μm) and 3 weight % components glass fibre (avarage fiber diameter：11 μm, average fiber length：30 μm), except this with Outside, catalyst is being prepared under the same conditions with catalyst 1, so as to obtain the catalyst 4 of the present invention.The abrasion of catalyst 4 It is 2.7kgf (26.5N) to spend for 0.13 weight %, hardness.

Embodiment 5

(preparation of catalyst 5)

It with the addition of the crystallinity cellulose (average grain diameter of 5 weight % components to the precalcining powder obtained in embodiment 1： 89.3 μm) and the silane treatment of 3 weight % components after glass fibre (avarage fiber diameter：11 μm, average fiber length： 50 μm), in addition, catalyst is being prepared under the same conditions with catalyst 1, so as to obtain the catalyst 5 of the present invention.Urge The wear intensity of agent 5 is 0.56 weight %, and hardness is 2.9kgf (28.4N).

Embodiment 6

(preparation of catalyst 6)

It with the addition of the crystallinity cellulose (average grain diameter of 5 weight % components to the precalcining powder obtained in embodiment 1： 89.3 μm) and 3 weight % components glass fibre (avarage fiber diameter：11 μm, average fiber length：3000 μm), except this In addition, catalyst is being prepared under the same conditions with catalyst 1, so as to obtain the catalyst 6 of the present invention.The mill of catalyst 6 Damage degree is 0.15 weight %, and hardness is 2.5kgf (24.5N).

Embodiment 7

(preparation of catalyst 7)

It with the addition of the crystallinity cellulose (average grain diameter of 5 weight % components to the precalcining powder obtained in embodiment 1： 89.3 μm) and 3 weight % components glass fibre (avarage fiber diameter：10 μm, average fiber length：300 μm), except this with Outside, catalyst is being prepared under the same conditions with catalyst 1, so as to obtain the catalyst 7 of the present invention.The abrasion of catalyst 7 It is 4.1kgf (40.2N) to spend for 0.27 weight %, hardness.

Embodiment 8

(preparation of catalyst 8)

It with the addition of the crystallinity cellulose (average grain diameter of 5 weight % components to the precalcining powder obtained in embodiment 1： 89.3 μm) and 3 weight % components glass fibre (avarage fiber diameter：10 μm, average fiber length：1500 μm), except this In addition, catalyst is being prepared under the same conditions with catalyst 1, so as to obtain the catalyst 8 of the present invention.The mill of catalyst 8 Damage degree is 0.29 weight %, and hardness is 2.7kgf (26.5N).

Comparative example 1

(preparation of catalyst 9)

Crystallinity cellulose (the average grain diameter of 5 weight % components is added to the precalcining powder obtained in embodiment 1： 89.3 μm), it is sufficiently mixed, then in comminution granulation is rotated, has been used relative to 33 that precalcining powder is 40 weight % Weight % glycerites in addition, are preparing catalyst, so as to obtain under the same conditions as binding agent with catalyst 1 The catalyst 9 that compares.The wear intensity of catalyst 9 is 0.31 weight %, and hardness is 1.6kgf (15.7N).

Comparative example 2

(preparation of catalyst 10)

Crystallinity cellulose (the average grain diameter of 5 weight % components is added to the precalcining powder obtained in embodiment 1： 89.3 μm) and 3 weight % components talcum (average grain diameter：57 μm), be sufficiently mixed, then in comminution granulation is rotated and Use relative to the 33 weight % glycerites that precalcining powder is 40 weight % as binding agent, in addition, with urging Agent 1 prepares catalyst under the same conditions, so as to obtain the catalyst 10 compared.The wear intensity of catalyst 10 is 0.20 Weight %, hardness are 1.4kgf (13.7N).

Comparative example 3

(preparation of catalyst 11)

It with the addition of the talcum (average grain diameter of 3 weight % components to the precalcining powder obtained in embodiment 1：57 μm), remove Beyond this, catalyst is being prepared under the same conditions with catalyst 1, so as to obtain the catalyst 11 compared.Catalyst 11 Wear intensity be 0.24 weight %, hardness is 1.9kgf (18.6N).

Comparative example 4

(preparation of catalyst 12)

To the completely no addition auxiliary agent of precalcining powder obtained in embodiment 1, in addition, identical with catalyst 1 Under conditions of prepare catalyst, so as to obtain the catalyst 12 compared.The wear intensity of catalyst 12 is 0.48 weight %, firmly Spend for 2.3kgf (22.5N).

Test example 1

(coke evolution reaction)

The catalyst 1 obtained by the following method in reaction evaluating embodiment 1.53ml catalyst is filled in stainless steel Reaction tube, is 1- butylene using gas volume ratio:Oxygen:Nitrogen:Vapor=1:1:7:1 mixed gas, under normal pressure, When GHSV1200 is small^-1Under conditions of, so as to keeping the mode of 1- butene conversion=80.0 ± 1.0% to change reaction bath temperature Degree, carries out reaction until when TOS300 is small, coke shape material is separated out on a catalyst.Exported in reaction tube, utilize condenser Liquid component is separated with gas componant, each component in gas componant is passed with flame ionization ditector and heat is provided with The gas-chromatography for leading detector has each carried out quantitative analysis.Factor correction is carried out to each data obtained using gas-chromatography, Calculate 1- butene conversions and butadiene selection rate.The small butadiene selection rates at present of TOS280 are 88.1%.

(coke combustion reaction)

After coke evolution reaction, for purpose of the precipitation in the coke shape substance combustion of catalyst is made, by reactive bath technique Temperature is set as 400 DEG C, the use of gas volume ratio is oxygen:Nitrogen=1:3 mixed gas, under normal pressure, in air speed 400 Hour^-1And TOS about 10 it is small when under conditions of, make coke shape substance combustion.The quantitative analysis same with coke evolution reaction is carried out, CO in reaction tube exit gas₂And the time point of the growing amount vanishing of CO, judge that the burning of coke shape material terminates.

(breakage rate evaluation)

After coke combustion reaction, the catalyst after reaction is taken out from reaction tube, is carried out using the sieve of 3.35mm Classification.The damaged catalyst to fragment shape and powdery fallen under sieve is weighed as catalyst plate, by with following formula The breakage rate as caused by long term test of the catalyst 1 calculated is 0.91 weight %.

Catalyst filling weight (g) before the weight (g) of breakage rate (weight %)=catalyst plate/coke evolution reaction × 100

Test example 2

The catalyst 3 that the catalyst to be evaluated in test example 1 is set as obtaining by embodiment 3, in addition, The evaluation of the breakage rate as caused by long term test has been carried out under same reaction conditions.The breakage rate of catalyst 3 is 0.12 weight %. The small butadiene selection rates at present of TOS280 are 88.3%.

Comparative test example 1

The catalyst 9 that the catalyst to be evaluated in test example 1 is set as obtaining by comparative example 1, in addition, The evaluation of the breakage rate as caused by long term test has been carried out under same reaction conditions.The breakage rate of catalyst 9 is 1.55 weight %. The small butadiene selection rates at present of TOS280 are 87.1%.

Comparative test example 2

The catalyst 11 that the catalyst to be evaluated in test example 1 is set as obtaining by comparative example 3, in addition, The evaluation of the breakage rate as caused by long term test has been carried out under the same reaction conditions.The breakage rate of catalyst 11 is 1.86 weights Measure %.The small butadiene selection rates at present of TOS280 are 86.6%.

Comparative test example 3

The catalyst 12 that the catalyst to be evaluated in test example 1 is set as obtaining by comparative example 4, in addition, The evaluation of the breakage rate as caused by long term test has been carried out under the same reaction conditions.The breakage rate of catalyst 12 is 1.16 weights Measure %.The small butadiene selection rates at present of TOS280 are 87.4%.

Table 1 shows wear intensity, hardness and the breakage obtained by embodiment, comparative example, test example and comparative test example The result of rate.By table 1, it will be apparent that, by adding the glass fibres inorganic assistant of the present invention, hardness improves, by not adding Organic additive, can significantly further improve the hardness of catalyst.The catalyst that hardness further improves can significantly press down The breakage rate as caused by long reaction is made, implys that the catalyst of the present invention can improve the long-time stability of reaction.For urging For agent 9, although wear intensity is good, but the breakage of the catalyst as caused by long reaction observed.In addition, according to The comparison of catalyst 3 and catalyst 9, obtains as drawn a conclusion：From significantly show with the catalyst as caused by long reaction From the viewpoint of damaged correlation, compared with wear intensity is evaluated, hardness be evaluated as it is tightened up to the long-time stability of reaction and Suitable evaluation of physical property method.That is, according to the present invention it will be apparent that, although not being known to those skilled in the art , but as with the damaged evaluation of physical property method with correlation as caused by long reaction, it is conventional as mechanical strength The wear intensity of evaluation method is not preferred, and hardness is preferable.

Claims (according to the 19th article of modification of treaty)

A kind of (1. after modification) conjugated diene manufacture formed catalyst, it is for being reacted by catalytic oxidative dehydrogenation by wrapping The catalyst of the monoolefine of carbon atom quantity more than 4 and the mixed gas manufacture conjugated diene of molecular oxygen, it is characterised in that The conjugated diene manufacture formed catalyst by by metal composite oxide and glass fibres inorganic assistant shape and Obtain, and metal composite oxide meets following composition formulas (D)：

Mo_l2Bi_aFe_bCo_cNi_dX_eY_fZ_g (D)

(in formula, X represents to represent selected from magnesium, calcium, strontium, barium selected from least one of lithium, sodium, potassium, rubidium, caesium alkali metal, Y At least one of alkali earth metal, Z represent in lanthanum, cerium, praseodymium, neodymium, samarium, europium, antimony, tungsten, lead, zinc, cerium, thallium at least A kind of element, a, b, c, d, e and f each represent bismuth, iron, cobalt, nickel, X, Y and Z relative to molybdenum 12 atomic ratio, in 0.3 ＜ a ＜ 3.5,0.6 ＜ b ＜ 3.4,5 ＜ c ＜ 8,0 ＜ d ＜ 3,0 ＜ e ＜ 0.5,0≤f≤4.0, the scope of 0≤g≤2.0, g are Meet the numerical value of the state of oxidation of other elements).

2. conjugated diene manufacture formed catalyst as claimed in claim 1, it is characterised in that the conjugated diene system Make the condition for meeting following formula (A) with formed catalyst：

R (=La/Dc)≤45 (A)

(in formula, La is the average fiber length of glass fibres inorganic assistant, and Dc is the average grain diameter of metal composite oxide).

3. conjugated diene manufacture formed catalyst as claimed in claim 1 or 2, wherein, the conjugated diene manufacture Organic additive is free of with formed catalyst.

(4. deletion)

(5. after modification) with formed catalyst is loaded, it is for conjugated diene manufacture as claimed any one in claims 1 to 3 For being manufactured altogether by the mixed gas of the monoolefine comprising carbon number more than 4 and molecular oxygen by catalytic oxidative dehydrogenation reaction The catalyst of yoke alkadienes, it is characterised in that metal composite oxide and glass fibres inorganic assistant are carried on carrier and Obtain.

A kind of (6. after modification) manufacture method of conjugated diene manufacture formed catalyst, it is claims 1 to 3 and right It is required that the manufacture method of the conjugated diene manufacture formed catalyst any one of 5, wherein, the manufacture method includes Following process：

The compound comprising each metal containing metal composite oxide is prepared more than 20 DEG C and under conditions of less than 90 DEG C Mixed solution or slurry, are then dried the mixture, carry out precalcining, together with glass fibres inorganic assistant into Shape, is formally calcined.

7. the manufacture method of conjugated diene manufacture formed catalyst as claimed in claim 6, wherein, the temperature of precalcining For more than 200 DEG C and less than 600 DEG C, and formal calcining heat is more than 200 DEG C and less than 600 DEG C.

8. the manufacture method of conjugated diene manufacture load formed catalyst as claimed in claims 6 or 7, it has will be multiple Close the forming process that metal oxide and glass fibres inorganic assistant are coated on carrier together with binding agent, and catalytic activity into Point load factor be more than 20 weight % and below 80 weight %, and the average grain diameter of catalyst be more than 3.0mm and Below 10.0mm.

9. the manufacture method of the formed catalyst as any one of claim 6 to 8, wherein, in whole manufacturing process, Without using organic additive.

Illustrate or state (according to the 19th article of modification of treaty)

Having carried out will added to right by the important document " metal composite oxide meets following composition formulas (D) " of claim 4 Ask the modification in 1.The 20th row of page 4 of the specification when modification is based on application is to the 11st row of page 6 and the 15th row of page 8 To the 24th row (the PCT publication paragraphs of page 8【0013】And【0021】) described in item.

Delete claim 4.

Claim 5 quotes any one of Claims 1 to 4, but due to deleting claim 4, is revised as drawing With any one of claims 1 to 3.

Claim 6 quotes any one of Claims 1 to 5, but due to deleting claim 4, is revised as drawing With any one of claims 1 to 3 and claim 5.

Claims (9)

1. a kind of conjugated diene manufacture formed catalyst, it is for being reacted by catalytic oxidative dehydrogenation by including carbon atom The catalyst of the monoolefine of number more than 4 and the mixed gas manufacture conjugated diene of molecular oxygen, it is characterised in that the conjugation Alkadienes manufacture formed catalyst is obtained by the way that metal composite oxide is shaped with glass fibres inorganic assistant.

2. conjugated diene manufacture formed catalyst as claimed in claim 1, it is characterised in that the conjugated diene system Make the condition for meeting following formula (A) with formed catalyst：

R (=La/Dc)≤45 (A)

(in formula, La is the average fiber length of glass fibres inorganic assistant, and Dc is the average grain diameter of metal composite oxide).

3. conjugated diene manufacture formed catalyst as claimed in claim 1 or 2, wherein, the conjugated diene manufacture Organic additive is free of with formed catalyst.

4. conjugated diene manufacture formed catalyst as claimed any one in claims 1 to 3, wherein, composition metal oxygen Compound meets following composition formulas (D)：

Mo_l2Bi_aFe_bCo_cNi_dX_eY_fZ_g (D)

(in formula, X represents to represent selected from magnesium, calcium, strontium, barium selected from least one of lithium, sodium, potassium, rubidium, caesium alkali metal, Y At least one of alkali earth metal, Z represent in lanthanum, cerium, praseodymium, neodymium, samarium, europium, antimony, tungsten, lead, zinc, cerium, thallium at least A kind of element, a, b, c, d, e and f each represent bismuth, iron, cobalt, nickel, X, Y and Z relative to molybdenum 12 atomic ratio, in 0.3 ＜ a ＜ 3.5,0.6 ＜ b ＜ 3.4,5 ＜ c ＜ 8,0 ＜ d ＜ 3,0 ＜ e ＜ 0.5,0≤f≤4.0, the scope of 0≤g≤2.0, g are Meet the numerical value of the state of oxidation of other elements).

5. conjugated diene manufacture load formed catalyst according to any one of claims 1 to 4, it is for passing through Catalytic oxidative dehydrogenation reaction manufactures conjugated diene by the mixed gas of the monoolefine comprising carbon number more than 4 and molecular oxygen Catalyst, it is characterised in that metal composite oxide is carried on carrier with glass fibres inorganic assistant and is obtained.

6. a kind of manufacture method of conjugated diene manufacture formed catalyst, it is any one of claim 1 to 5 The manufacture method of conjugated diene manufacture formed catalyst, wherein, the manufacture method includes following process：

The compound comprising each metal containing metal composite oxide is prepared more than 20 DEG C and under conditions of less than 90 DEG C Mixed solution or slurry, are then dried the mixture, carry out precalcining, together with glass fibres inorganic assistant into Shape, is formally calcined.

7. the manufacture method of conjugated diene manufacture formed catalyst as claimed in claim 6, wherein, the temperature of precalcining For more than 200 DEG C and less than 600 DEG C, and formal calcining heat is more than 200 DEG C and less than 600 DEG C.

8. the manufacture method of conjugated diene manufacture load formed catalyst as claimed in claims 6 or 7, it has will be multiple Close the forming process that metal oxide and glass fibres inorganic assistant are coated on carrier together with binding agent, and catalytic activity into Point load factor be more than 20 weight % and below 80 weight %, and the average grain diameter of catalyst be more than 3.0mm and Below 10.0mm.

9. the manufacture method of the formed catalyst as any one of claim 6 to 8, wherein, in whole manufacturing process, Without using organic additive.